Energy dependent saturable and reverse saturable absorption in cube-like polyaniline/polymethyl methacrylate film

Solid films of cube-like polyaniline synthesized by inverse microemulsion polymerization method have been fabricated in a transparent PMMA host by an in situ free radical polymerization technique, and are characterized by spectroscopic and microscopic techniques. The nonlinear optical properties are studied by open aperture Z-scan technique employing 5 ns (532 nm) and 100 fs (800 nm) laser pulses. At the relatively lower laser pulse energy of 5 μJ, the film shows saturable absorption both in the nanosecond and femtosecond excitation domains. An interesting switchover from saturable absorption to reverse saturable absorption is observed at 532 nm when the energy of the nanosecond laser pulses is increased. The nonlinear absorption coefficient increases with increase in polyaniline concentration, with low optical limiting threshold, as required for a good optical limiter.     

Ultrafast optical nonlinearity of titanylphthalocyanine films

The optical properties of titanylphthalocyanine (TiOPc) thin film fabricated by physical jet deposition technique were investigated by using absorption, femtosecond (fs) optical Kerr effect (OKE) and fs pump–probe techniques. The third-order nonlinear optical susceptibility of TiOPc film was measured to be 3×10⁻¹⁰ esu. The OKE response of TiOPc films shows a decay process with subpicosecond time constant, demonstrating that the excited state of TiOPc molecule has little contribution to the photo-induced birefringence. From the fs pump–probe experiment, a complicated decay behavior with three decay components was observed, which originates from the contribution of exciton–exciton annihilation process, the enhanced intersystem crossing process and the relaxation of the triplet state.     

Optical,structural and electrochromic behavior studies on nanocomposite thin film of aniline,o-toluidine and WO3

In the field of materials for electrochromic (EC) applications much attention was paid to the derivatives of aniline. We report on the optical, structural and electrochromic properties of electrochromic thin film based on composite of WO₃ nanoparticles and copolymer of aniline and o-toluidine prepared by electrochemical polymerization method on fluorine doped tin oxide (FTO) coated glass. The thin film was studied by X-ray diffraction (XRD) and Fourier transforms infrared (FTIR) spectroscopy. The morphology of prepared thin film was characterized by field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM) and the thermal gravimetric analysis (TGA) as well. The optical spectra of nanocomposite thin film were characterized in the 200–900 nm wavelength range and EC properties of nanocomposite thin film were studied by cyclic voltammetry (CV). The calculation of optical band gaps of thin film exhibited that the thin film has directly allowed transition with the values of 2.63 eV on first region and 3.80 eV on second region. Dispersion parameters were calculated based on the single oscillator model. Finally, important parameters such as dispersion energy, oscillator energy and lattice dielectric constant were determined and compared with the data from other researchers. The nonlinear optical properties such as nonlinear optical susceptibility, nonlinear absorption coefficient and nonlinear refractive index were extracted. The obtained results of nanocomposite thin film can be useful for the optoelectronic applications.     

Third-order nonlinear optical responses of nanoparticulate Co3O4 films

Third-order nonlinear optical responses of nanoparticulate Co₃O₄ films, prepared by sputtering and pyrolysis, were investigated. The sputtered Co₃O₄ film showed a large third-order nonlinear susceptibility (|χ⁽³⁾|) of 3.2×10⁻⁸ esu, determined by degenerate four-wave mixing (DFWM). This |χ⁽³⁾| is 7.1 times greater than that of the pyrolyzed Co₃O₄ film, attributable to the greater density and refractive index of the sputtered film. Time-resolved DFWM experiments show a slowly decaying component with a lifetime of approximately 100 ps existing for both films in addition to a fast decaying component. Nonlinear transmission experiments revealed both films exhibiting significant nonlinear absorption. The imaginary part of the susceptibility (Im[χ⁽³⁾]) found for each film was of the same order of magnitude as the |χ⁽³⁾| found by the DFWM method, showing that the major part of the fast decaying component of |χ⁽³⁾| comes from the nonlinear absorption.     

Nonlinear characteristic and optical limiting effect of oil red O azo dye in liquid and solid media

In view of a possible application in optical limiting devices for protection against laser radiation, the nonlinear optical absorption, refraction and optical limiting behavior of an organic dye, oil red O, under excitation with CW, Nd: YAG laser at 532 nm was studied. The nonlinear optical responses of the dye were studied both in solution (acetonitrile) and solid film, (methylmethacrylate [MMA]) respectively, using the single-beam Z-scan technique. The open aperture Z-scan of the solution and solid samples displayed reversible saturable absorption. The closed aperture Z-scan of the samples exhibited negative nonlinearity, which was larger in magnitude in the solid film compared to that in solution. The nonlinear refractive index was found to vary with concentration. Optical limiting characteristics of the dye at various concentrations were studied. The third-order nonlinearity of this dye is dominated by nonlinear absorption, which leads to strong optical limiting of the laser.     

Indium(III) and Gallium(III) phthalocyanines-based nanohybrid materials for optical limiting

Linear and nonlinear optical properties of a phthalocyanine (Pc)-based nanohybrid material PCIGS [Cu₂(tBu₄PcGa)(tBu₄PcIn)S₂TPP₂] are described. The overall aggregation of phthalocyanines in poly(methylmethacrylate) (PMMA) films was evident, which is indicated by the broadening of linear spectra in the Q-band region and the shift of wavelength. Upon excitation with nanosecond laser pulse at 355 nm, the transient absorption band appeared at about 500 nm is attributed to the triplet–triplet absorption of the Pcs. For PCIGS and its starting materials tBu₄PcGaCl and tBu₄PcInCl, all Z-scans exhibit a decrease in transmittance about the focus typical of an induced positive nonlinear absorption of incident light. The absorption mechanism is due to population of excited states through a multi-step nonlinear absorption. When these Pc compounds were embedded into a commercially available polymer PMMA, all the Pc/PMMA composites display much larger nonlinear absorption coefficient and lower saturable fluence for optical limiting when compared to the same Pc molecules in solution. However, in contrast to tBu₄PcGaCl and tBu₄PcInCl, PCIGS displayed decreased optical limiting response, possibly due to competing electron accepting processes in the In and Ga metals, and the highly ordered structure of the PCIGS complex itself.     

Third-order optical nonlinearity of cadmium sulfide nanoparticles loaded in mesostructured silica materials

Cadmium sulfide nanoparticles have been successfully incorporated in three forms of CTAB-templated mesoporous silica materials: one is the mesoporous silica spheres suspended in ethanol solution, the other is the mesoporous silica spheres spin-coated on glass slide, and the third is the dip-coated mesoporous silica thin film. The mesostructures were characterized by XRD and TEM, respectively. Linear optical properties were investigated using UV-visible spectra, and the diameter of the incorporated CdS nanoparticles was measured to be around 3.1 nm. Z-scan technique manifested that these three composites exhibited distinct third-order optical nonlinearities due to the different preparation techniques. Reverse saturation absorption could be detected in the CdS-loaded mesoporous silica spheres suspended in solution, while those dispersed on glass slide presented saturation absorption. The difference in nonlinear absorption of the two mesoporous silica sphere samples could be attributed to defect-related transitions. On the contrary, the CdS-loaded mesoporous silica thin film showed self-defocusing behavior with no nonlinear absorption signals. Compared to that of the CdS nanoparticles with larger size previously reported, the intrinsic microscopic third-order nonlinear optical susceptibility of those incorporated in CTAB-templated mesoporous thin film was increased as predicted by the quantum theory, and the third-order optical nonlinearity was further determined to arise from intraband transitions induced by quantum confinement.     

Large nonlinear optical response of a Bi1.5Zn1.0Nb1.5O7 thin film fabricated by pulsed laser deposition

The Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin film has been fabricated on MgO (001) substrate by pulsed laser deposition. The nonlinear optical properties of the BZN film were investigated using Z-scan technique at a wavelength of 532 nm with 25 ps pulse duration. The two-photon absorption coefficient and the nonlinear refractive index of the BZN film were obtained to be 4.2 × 10^− 6 cm/W and 1.6 × 10^− 10 cm²/W respectively, which are comparable with those of some representative nonlinear optical materials. The large and fast response optical nonlinearities indicated that the BZN film is a promising candidate for future photonics devices.     

Properties of cu-doped low resistive ZnSe films deposited by two-sourced evaporation

Two-sourced evaporation technique is used to prepare hard ZnSe films by controlling the evaporation rates of both Zn and Se at substrate temperature of 400 °C. The films are doped with Cu by immersion in the Cu(NO₃)₂-H₂O solution for different periods of time. The XRD has not shown a drastic change in the film structure while the electrical resistivity of the deposited film dropped from 10⁹ Ω-cm to about 1.6 Ω-cm for solution immersed films after heat treatment. Optical properties of deposited and doped films, such as film thickness, absorption coefficient and optical band gap have been calculated from the normal transmission spectra in the range of 300-2200 nm.The optical results show a decrease of the transmission and an increase of the refractive index and a slight shift in the optical band gap. Chemical composition of the Cu is determined by using absorption of immersed films. The composition of Cu is also compared with the composition detected by electron microprobe analyzer (EMPA).     

Nonlinear optical and optical limiting properties of phthalocyanines in solution and thin films of PMMA at 633 nm studied using a cw laser

We present our results on nonlinear optical (NLO) and optical limiting properties of Tetra tert-butyl phthalocyanine and Zinc tetra tert-butyl phthalocyanine studied at 633 nm using a continuous wave laser. We have evaluated the sign and magnitude of the third-order nonlinearity from the closed aperture Z-scan data while the nonlinear absorption properties were assessed using the open aperture data. We have observed low power optical limiting, with low limiting thresholds, based on nonlinear refraction in both the samples. We also present results on the NLO properties of the same dyes doped in Polymethylmethacrylate (PMMA). These studies indicate that both the phthalocyanines are potential candidates for low power optical limiting applications.     

Optical properties of double-layer structure phthalocyanine–tetracyanoquinodimethane

Optical properties of double-layer structures consisting of Cu-phthalocyanine vacuum evaporated film and Langmuir–Blodgett film of pentadecyl-7,7,8,8-tetracyano-1,4-quinodimethane (pentadecyl-TCNQ) were investigated by ellipsometry and optical transmission. The obtained results indicate strong interaction between the materials; the resulting optical properties cannot be presented as the sum of those of the particular components. Two new effective absorption bands at 1.08 and 2.85 eV were found for such structures. The band at 2.85 eV coincides with a measured peak in photocurrent spectrum, which supports the idea on a charge transfer complex formation between Cu-phthalocyanine to TCNQ.     

Role of precursors on morphology and optical properties of ZnS thin films prepared by chemical spray pyrolysis

This study investigates the effect of different growth parameters on the structural and optical properties of ZnS thin films, prepared using spray pyrolysis. The films were prepared using different Zn:S ratios (between 1:1 and 1:6) and in different growth solutions: (A), zinc chloride and thiourea and (B) dehydrated zinc acetate and thiourea, both in distilled water.By varying the Zn:S ratio in the films, the optical properties (absorption and photoluminescence) show that different species are created during film growth. This was deduced from the wide emission band appearing in the green region of the photoluminescence spectra, and from the change in band gap, which varies between 3.2 and 3.5 eV. Films formed from solution (A) with a Zn:S ratio of 1:3 or 1:4 show the best morphology and transmission. ZnS has a wider band gap than other conventional II-VI semiconductors utilized in various electronic and optical devices and can be expected to provide a useful window layer of solar cells which leads to an improvement in overall efficiency by decreasing absorption loss.     

Thickness dependence of structural and optical properties of indium tin oxide nanofiber thin films prepared by electron beam evaporation onto quartz substrates

Indium tin oxide (ITO) thin films, produced by electron beam evaporation technique onto quartz substrates maintained at room temperature, are grown as nanofibers. The dependence of structural and optical properties of ITO thin films on the film thickness (99-662 nm) has been reported. The crystal structure and morphology of the films are investigated by X-ray diffraction and scanning electron microscope techniques, respectively. The particle size is found to increase with increasing film thickness without changing the preferred orientation along (2 2 2) direction. The optical properties of the films are investigated in terms of the measurements of the transmittance and reflectance determined at the normal incidence of the light in the wavelength range (250-2500 nm). The absorption coefficient and refractive index are calculated and the related optical parameters are evaluated. The optical band gap is found to decrease with the increase of the film thickness, whereas the refractive index is found to increase. The optical dielectric constant and the ratio of the free carrier concentration to its effective mass are estimated for the films.     

Optical second harmonic generation in a low-bandgap polymer

Recently, much research has been performed on developing low-bandgap polymers for e.g. harvesting solar energy. In the quest to improve these properties, little attention has been paid to their nonlinear optical properties, despite their interesting linear optical spectra and structural similarities to certain nonlinear optically active compounds. We characterized the optical second harmonic generation of corona poled films of poly(cyclopenta[2,1-b;3,4-b′] dithiophen-4-ylidenedioctylmalonate). The unexpectedly large nonlinear optical susceptibilities and the thermal and temporal stability of the material compare favorably to other novel nonlinear optical materials despite the lack of a donor-acceptor dye. Additionally, the polymer displays a very low absorption in the relevant wavelength region. These results demonstrate the promise of these materials for nonlinear optical devices.     

Role of the deposition parameters and aging on the optical and photoluminescence properties of C70 films

We have investigated the influence of the growth parameters (substrate temperature and deposition rate) and the aging process on the optical properties of C₇₀ thin films, by means of absorption and photoluminescence spectra. The Urbach energy, obtained from the absorption spectra, indicates that the substrate temperature influences the film optical properties more than the deposition rate. The luminescence spectra suggest the important role of the disorder in the radiative efficiency. The main structures of the emission spectra have been assigned to an intramolecular polaron-exciton. The analysis of the temperature dependence of the photoluminescence spectra of the as-deposited samples shows that the vibronic transitions are dominant at low temperature, whereas the singlet purely electronic recombination (due to Frenkel-type exciton) is visible at a sufficiently high temperature. On the contrary, in the aged samples this purely electronic transition is well resolved from low to high temperature. This anomalous behaviour is discussed and attributed to the disorder introduced in the film.     

Synthesis,surface profile,nonlinear reflective index and photophysical properties of curcumin compound

Curcumin and other three curcuminoids (bisdemethoxycurcumin, α-chlorocurcumin and α-methylcurcumin) were synthesized. Fourier transform infrared spectroscopy, Fluorescence quantum yields, AFM analysis and image surface profiles were characterized. All compounds possessed electron donor moieties at both ends of the conjugated π-system and an electron acceptor moiety in the middle of the molecules (D-A-D system) and should exhibit different optical properties depending on substituents on the benzene rings. The third order nonlinear optical properties of the curcuminoids have been investigated by z-scan technique. The optical response was characterized by measuring the refractive index (n₂) of the derivatives of curcumin using the Z-scan technique. The compounds showed negative and large nonlinear refractive index values of the order of 10^?7 cm²/W and reverse saturable absorption with high values of the nonlinear absorption coefficient of the order of 10^?4 cm/W. The nonlinear refractive index was found to vary with the different compound. The optical constants of the different compound films were studied and the dispersion of the refractive index was discussed in terms of the Wemple-DiDomenico single oscillator model. The photo-physical properties of these compounds are compared to those of native curcumin, in order to provide a rationale to the design of samples with molecular structures optimized for a photosensitizer. These types of materials may be considering new photonic applications.     

Studies on phase transformation and molecular orientation in nanostructured zinc phthalocyanine thin films annealed at different temperatures

Studies on the electronic and optical properties of thin films of organometallic compounds such as phthalocyanine are very important for the development of devices based on these compounds. The nucleation and grain growth mechanism play an important role for the final electronic as well as optoelectronic properties of the organic and organometallic thin films. The present article deals with the change in the film morphology, grain orientation of nanocrystallites and optical properties of zinc phthalocyanines (ZnPc) thin films as a function of the post deposition annealing temperature. The effect of annealing temperature on the optical and structural property of vacuum evaporated ZnPc thin films deposited at room temperature (30 °C) on quartz glass and Si(100) substrates has been investigated. The thin films have been characterized by the UV-vis optical absorption spectra, X-ray diffraction (XRD), atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy. From the studies of UV-vis absorption spectra and XRD data, a metastable α to β-phase transformation has been observed when the thin films were annealed at a temperature greater than about 250 °C. The FESEM images have shown the particlelike structure at room temperature and the structure became rodlike when the films were annealed at high temperatures. TEM image of ZnPc film dissolved in ethanol has shown spectacular rod-shaped crystallites. High resolution transmission electron microscopy image of a single nanorod has shown beautiful “honey-comb” like structure. Particle size and root mean square roughness were calculated from AFM images. The changes in band gap energy with increase in annealing temperature have been evaluated.     

Large nonlocal nonlinear optical response of castor oil

The nonlocal nonlinearity of castor oil was investigated using the Z-scan technique in the CW regime at 514 nm and in femtosecond regime at 810 nm. Large negative nonlinear refractive indexes of thermal origin, thermo-optical coefficients and degree of nonlocality were obtained for both laser excitation wavelengths. The results indicate that the electronic part of the nonlinear refractive index and nonlinear absorption were negligible. Our results suggest that castor oil is promising candidate as a nonlinear medium for several nonlocal optical applications, such as in spatial soliton propagation, as well as a dispersant agent in the measurement of absorptive properties of nanoparticles.     

高三阶光学非线性Cd/CdS-SiO2复合薄膜的电化学–溶胶凝胶制备及表征

以硝酸镉、硫脲和正硅酸乙酯为前驱体, 采用电化学-溶胶凝胶法, 以ITO玻璃为基底制备了透明薄膜。扫描电子显微镜(SEM)表征表明薄膜为纳米束结构。X射线能谱(EDX)表征表明薄膜由Si、O、Cd、S元素组成, Cd/S(原子比)＞1。EDX表征结合循环伏安(CV)实验确定薄膜为Cd/CdS-SiO₂复合薄膜。Z扫描表征表明, 薄膜在1064 nm处表现出自散焦特性的非线性折射效应和饱和吸收特性的非线性吸收特性。薄膜的三阶非线性极化率(χ(3))较高, 达到了1.18×10^-14~1.39×10^-13 (m/V)², 表明薄膜具有优良的三阶光学非线性。分析认为薄膜中CdS的含量对薄膜的光学性非线性起主要作用。     

High-temperature-dependent optical properties of ZnO film on sapphire substrate

In order to fabricate fiber-optic temperature sensors based on ZnO film, it is important to study the temperature-dependent optical properties of this material. In this work, we deposited ZnO films on c-plane (0001) sapphire substrate at 250 °C. Atomic force microscope and X-ray diffraction measurements show the smooth surface and high orientation along [0001] of ZnO film, respectively. The high-temperature-dependent optical properties of ZnO film were measured by ultraviolet-visible transmission with temperatures ranging from room-temperature to 300 °C and analyzed by theoretically fitting the optical absorption edge curve. It is observed that the band gap energy red shifts nonlinearly from 3.345 to 3.153 eV with increasing temperature. The sharp absorption edge of ZnO films after annealing at 300 °C is almost consistent with that of the as-deposited sample, indicating an excellent thermal stability and the potential application in fiber-optic temperature sensors.